金属草酸盐基负极材料——离子电池储能材料的新选择

商业化锂离子电池石墨负极和锂盐过渡金属氧化物正极材料的储锂容量都已接近各自的理论值,探索下一代高能量密度电极材料是解决现阶段锂离子电池容量限制的关键。近年来,新型金属草酸基负极材料,借助其在金属离子电池中多元化储能机制诱发的较高储能效应在碱金属离子电池绿色储能材料领域备受关注。本文就金属草酸基材料在锂、钠、钾金属离子电池方面的最新研究进行了综述,着重介绍了材料的晶型结构、多元化储能机制及储能过程中的动力学特征,简单阐述了材料在电化学储能中存在的问题,分析了金属草酸基负极材料在形貌晶型控制、界面碳复合改性和金属元素掺杂方面的改性策略。最后,预测了金属草酸基负极材料在碱金属离子电池体系的发展方向。     

N-Doped Carbon Nanofibers Encapsulating CoO@Co9S8 Nanoparticles: Preparation from S-Rich Co32 Coordination Cluster Precursors by Electrospinning and Application for Superior Li-ion Storage

Thiacalixarene-supported Co₃₂nanoclusters encapsulated in polyacrylonitrile nanofibers(Co₃₂@PAN-NFs) by electrospinning have been utilized as precursors to fabricate N-doped CoO@Co₉S₈ carbon nanofibers(CoO@Co₉S₈@CNFs) for superior Li-ion storage. The S-rich Co₃₂ clusters capped by organic sheets afforded the well dispersed cobalt oxide/sulfide nanoparticles embedded in carbon nanofiber composites by direct calcination. The N-doped CoO@Co₉S₈@CNFs nanocomposites have been utilized as anode materials for lithium ion battery with the reversible capabilities being of 1051.8, 967.6, 894.7, 782.7, 669.5 and 525.4 mA·h/g at 0.1, 0.2, 0.5, 1, 2 and 3 A/g, respectively. The CoO@Co₉S₈@CNFs also showed a relatively high stable capacity of 551.7 mA·h/g at the current density of 1 A/g after 200 cycles of rate experiments. The as-obtained N-doped CoO@Co₉S₈@CNFs nanocomposites exhibited superior reversible capacity, rate performance, Coulomb efficiency(74.5% vs. 63.9%) and cyclic stability comparing with the CoO@Co₉S₈@C derived from simple annealing of Co₃₂ templates.     

Pesticidal potential of some wild plant essential oils against grain pests Tribolium castaneum (Herbst, 1797) and Aspergillus flavus (Link, 1809)

The red flour beetle, Tribolium castaneum, and the mold Aspergillus flavus are well known threats of stored grain commodities, causing nutritional loss and poisoning of stored products, respectively. T. castaneum has developed resistance against most insecticides, leading to the use of extensive amounts of synthetic insecticides to protect stored grains. Synthetic pesticides not only toxify the environment but also cause serious health issues in humans using pesticide treated grains. This study aimed to identify plant-based natural pesticides to control T. castaneum and A. flavus. Essential oils were extracted from fresh aerial parts of Chenopodium ambrosioides, Conyza sumatrensis, Erigeron canadensis, and Tagetes minuta through steam distillation and investigated for insecticidal and anti-fungal activities against adult T. castaneum and A. flavus, respectively. GC–MS analysis of C. sumatrensis revealed the presence of 37.7% cis-lachnophyllum ester, 13.4% germacrene D, and 21.6% limonene, whereas in E. canadensis the major compounds were limonene, germacrene D, and cis-lachnophyllum ester (43.4%, 12.9% and 5.9%, respectively). In bioassays with treated grain, C. sumatrensis and E. canadensis essential oils exhibited excellent toxicity against adult T. castaneum with LD₅₀ of 3.7 and 5.6 mg per 10 g grains whereas in a fumigation bioassay they showed LD₅₀ of 6.6 and 10.6 mg/L, respectively. The essential oils extracted from C. ambrosioides and E. canadensis exhibited good anti-fungal activity against A. flavus. Our findings suggest that essential oils of C. sumatrensis and E. canadensis can play an important role in protecting stored grains from T. castaneum and A. flavus contamination.     

Experimental and mechanistic study of mudstone volumetric swelling at the bottom of salt cavern gas storage

Salt cavern gas storage is one of the vital strategic natural gas reserves and emergency peak shaving facilities all over the world. However, rock salt in China is primarily bedded salt, usually composed of many thin salt layers and interlayers (e.g., anhydrite, mudstone, and glauberite). During the water solution mining process of the cavern, the insoluble mudstones fall to the bottom and account for 1/3 up to 2/3 of the storage capacity. The bulk volume of the insoluble mudstones is almost twice its in-suit volume. It is of great urgency to investigate the swelling mechanisms of the bottom insoluble mudstones. Given this, we first analyzed the mineral composition of salt rock and insoluble mudstones by using XRD and SEM methods. Then, experimental studies were carried out considering both clay swelling and physical packing. At last, the zeta potential tests were conducted to reveal the swelling mechanisms of the bottom mudstones. Results show that the volumetric expansion of mudstones is made up of three parts: clay swelling, particle surface bound water volume, and pore space free water volume increase. Because the content of expansive clay in the bottom mudstones is less than 2%, and the high salinity brine in the cavern has excellent clay stability performance, clay swelling is not the main contributor to the volumetric expansion of the bottom mudstones. Measurement results show that the surface of the mudstones is negatively charged after hydration. Electrostatic repulsion can increase the spacing between small rock particles and creates approximately 47.6% of the pore space, which is the main factor in the volumetric expansion of mudstones. This study provides a theoretical basis for the mining solution and capacity enlargement during the construction of bedded salt cavern gas storage in China.     

New Insight on Carbon Dioxide-Mediated Hydrogen Production**

A new approach to hydrogen production from water is described. This simple method is based on carbon dioxide-mediated water decomposition under UV radiation. The water contained dissolved sodium hydroxide, and the solution was saturated with gaseous carbon dioxide. During saturation, the pH decreased from about 11.5 to 7–8. The formed bicarbonate and carbonate ions acted as scavengers for hydroxyl radicals, preventing the recombination of hydroxyl and hydrogen radicals and prioritizing hydrogen gas formation. In the presented method, not yet reported in the literature, hydrogen production is combined with carbon dioxide. For the best system with alkaline water (0.2 m NaOH) saturated with CO₂ under UV-C, the hydrogen production amounted to 0.6 μmol h⁻¹ during 24 h of radiation.     

Recent advances in electrochemistry of pyridinium-based electrophores: A structronic approach

The context of molecular structronics (from “molecular structure” and “electronics”) is that of molecular-level electrochemical storage of energy of sustainable origin (wind, solar). Due to its discontinuous availability, storage of this energy is a key issue. The targeted type of storage relies on implementing “electron reservoirs” within the structronic molecules by electrochemically forming dedicated chemical bonds according to non-catalytic processes. Reservoir bonds are therefore integral parts of the molecular backbone of structronic assemblies. When filled, electron reservoirs manifest themselves in the form of elongated covalent bonds that are to be cleaved for electron releasing (discharging) on demand. The scope of this short review is limited to pyridinium electrophores as particularly suited building blocks for the development of structronics.     

Electrochemical hydrogen storage in porous carbons with acidic electrolytes: Uncovering the potential

Electrochemical hydrogen storage in porous carbon materials is emerging as a cost-effective hydrogen storage and transport technology with competitive power and energy densities. The merits of electrochemical hydrogen storage using porous conductive carbon-based electrodes are reviewed. The employment of acidic electrolytes in such storage systems is compared with alkaline electrolytes. The recent innovations of a proton battery for smaller-scale electricity storage, and a proton flow reactor system for larger (grid)-scale storage and bulk export of hydrogen produced from renewable energy, are briefly described. It is argued that such systems, along with variants proposed by others, all of which rely on electrochemical hydrogen storage in porous carbons, can contribute to the search for energy storage technologies essential for the transition to a zero-emission global economy.     

Eco friendly synthesis of fluorescent carbon dots for the sensitive detection of ferric ions and cell imaging

This study established a ferric ion (Fe³⁺) detection method as a result of the fluorescence quenching effect of Fe³⁺ on carbon dots (CDs). Specifically, we proposed, a green microwave synthesis route towards fluorescent CDs that requires only the brewer’s spent grain as starting materials. Transmission electron microscopy, X-ray diffraction, Fourier-transform infrared spectra and X-ray photoelectron spectroscopy were performed to investigate the CDs characteristic: morphology, size distribution, functional groups, and composition, respectively. The experimental results, which were run under optimal experimental conditions, indicated that the fluorescence intensity and concentration of Fe³⁺ were within the desired linear range (0.3–7 μM). The detection limit of this assay towards Fe³⁺ was 95 nM. The proposed method showed significant selectivity with respect to interfering ions. We evaluated the potential application of this method with tap water, lake water and fetal bovine serum as real samples. Additionally, the CDs could be served as superior bioimaging probes in Hela cells as a result of their excellent optical stability and good biocompatibility. In a word, the present study provides a new idea for CDs derived from the waste of agricultural products for detecting food or environmental contaminants and cell imaging.     

Redox targeting of energy materials

The redox-mediated electrochemical–chemical process, when it involves the redox-targeting reaction with energy materials, has shown intriguing potential for various energy-related applications. This review starts with a brief discussion on the evolution of redox-targeting reactions for high-energy redox-flow batteries and the critical future studies for large-scale energy storage. Then, with spatially decoupled water electrolysis as an example, the merits of redox-targeting reaction by liberating the catalyst from electrode surface are highlighted, followed by an introduction of redox targeting–based thermal-to-electrical conversion. We have also featured various redox-targeting processes in other fields of study, such as electrochromic window, redox catalysis, and spent battery material recycling. Overall, this review attempts to demonstrate the incredible versatility and prospects of redox-targeting process for energy-related applications.     

Spent Grain from Malt Whisky: Assessment of the Phenolic Compounds

In order to extract antioxidant phenolic compounds from spent grain (SG) two extraction methods were studied: the ultrasound-assisted method (US) and the Ultra-Turrax method (high stirring rate) (UT). Liquid to solid ratios, solvent concentration, time, and temperature/stirring rate were optimized. Spent grain extracts were analyzed for their total phenol content (TPC) (0.62 to 1.76 mg GAE/g SG DW for Ultra-Turrax pretreatment, and 0.57 to 2.11 mg GAE/g SG DW for ultrasound-assisted pretreatment), total flavonoid content (TFC) (0.6 to 1.67 mg QE/g SG DW for UT, and 0.5 to 1.63 mg QE/g SG DW for US), and antioxidant activity was measured using 2,2-diphenyl-2-picrylhydrazyl (DPPH) free radical (25.88% to 79.58% for UT, and 27.49% to 78.30% for UT). TPC was greater at a high stirring rate and high exposure time up to a certain extent for the Ultra-Turrax method, and at a high temperature for the ultrasound-assisted method. P-coumaric acid (20.4 ± 1.72 mg/100 SG DW for UT, and 14.0 ± 1.14 mg/100 SG DW for US) accounted for the majority of the phenolic found compounds, followed by rosmarinic (6.5 ± 0.96 mg/100 SG DW for UT, and 4.0 ± 0.76 mg/100 SG DW for US), chlorogenic (5.4 ± 1.1 mg/100 SG DW for UT, and non-detectable for US), and vanillic acids (3.1 ± 0.8 mg/100 SG DW for UT, and 10.0 ± 1.03 mg/100 SG DW for US) were found in lower quantities. Protocatechuic (0.7 ± 0.05 mg/100 SG DW for UT, and non-detectable for US), 4-hydroxy benzoic (1.1 ± 0.06 mg/100 SG DW for UT, and non-detectable for US), and caffeic acids (0.7 ± 0.03 mg/100 SG DW for UT, and non-detectable for US) were present in very small amounts. Ultrasound-assisted and Ultra-Turrax pretreatments were demonstrated to be efficient methods to recover these value-added compounds.